Cross-linked networks from multifunctional hyperbranched polymers

ABSTRACT

Hyperbranched polymers having a plurality of at least two different types of functional groups are described. Specific embodiments include hyperbranched polymers having functional groups of a first type that are substantially uniformly distributed throughout the hyperbranched polymer molecule and a second type of functional group that is substantially uniformly distributed at the terminals of the hyperbranched polymer molecule. The hyperbranched polymers having different types of functional groups are synthesized by reacting one or more monomers having functional groups that are capable of reacting during a set of polymerization conditions to form a hyperbranched polymer, wherein at least one of the monomers contains latent functional groups that are not reactive during polymerization.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. application Ser. No. 09/970,366entitled HYPERBRANCHED POLYMERS WITH LATENT FUNCTIONALITY AND METHODS OFMAKING SAME, filed Oct. 3, 2001 which issued Nov. 11, 2003 as U.S. Pat.No. 6,646,089, the entire disclosure of which is incorporated herein byreference.

FIELD OF THE INVENTION

This invention relates to hyperbranched polymers having different typesof reactive functional groups and methods of preparing hyperbranchedpolymers having different reactive functional groups.

BACKGROUND OF THE INVENTION

Hyperbranched polymers are tree-like macromolecules that possess moreextensive chain branching than traditional branched polymers containingmostly primary and secondary branches attached primarily to linearmain-chain backbones, but less extensive and regular than perfectlybranched dendrimers. In other words, hyperbranched polymers have amolecular architecture that is intermediate between traditional branchedpolymers and ideally branched dendrimers.

While several different types of dendrimers containing differentreactive functional groups have been prepared by various syntheticstrategies, no such counterparts have been reported for hyperbranchedpolymers. A notable exception to this is hyperbranched macromoleculesthat result from AB_(x) polymerization and that ideally contain a singleA group in the focal point, if cyclization is suppressed. However, thissingle functional group per hyperbranched polymer molecule may not beavailable for further reaction due to such factors as steric hindranceand intramolecular cyclization, and the single functional group isnormally present at a negligible concentration such that it generallydoes not have any utility. Therefore, hyperbranched polymers having aplurality of different functional groups per molecule, and particularlytwo different functional groups that are reactive under differentconditions, are presently unknown.

SUMMARY OF THE INVENTION

This invention pertains to hyperbranched polymers having a plurality ofeach of at least two different types of functional groups.

In one aspect of the invention, the two different functional groups, arereactive under different conditions. In other words, a first type offunctional group is reactive and a second type of functional group isnot reactive under a first set of conditions, and the first type offunctional group is not reactive and the second type of functional groupis reactive under a second set of conditions. This allows the first typeof functional group to be used for one purpose, such as forcross-linking the hyperbranched polymer molecules to form a networkstructure, and the second type of functional group for another purpose,such as to form a nanoscopic domain which can act as a particle-likereinforcing agent within the hyperbranched polymer network. In additionto this, the second type of functional group can also be used forattachment of a variety of species, such as molecules of drugs, markers,sensors, catalysts, etc.

Other aspects of the invention relate to cross-linked polymer networkscontaining hyperbranched domains having a plurality of each of at leastone type of functional groups: cross-linked polymer networks containinga nanoscopic inorganic reinforcing agent covalently bonded to thepolymer network, hyperbranched polymers containing nanoscopic inorganicparticles distributed in and covalently bonded to the hyperbranchedpolymer, methods of synthesizing hyperbranched polymers having aplurality of each of at least two different types of functional groups,methods of forming cross-linked polymer networks from hyperbranchedpolymers having a plurality of each of at least two different types offunctional groups, methods of preparing cross-linked polymer networkscontaining a nanoscopic reinforcing agent covalently bonded to thepolymer network, and methods of preparing hyperbranched polymerscontaining nanoscopic inorganic particles distributed in and covalentlybonded to the hyperbranched polymer.

These and other features, advantages and objects of the presentinvention will be further understood and appreciated by those skilled inthe art by reference to the following specification and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of the formation of aninter-domained cross-linked network accompanied by and/or followed byintra-domain cross-linking through latent functionalities (HBP:hyperbranched polymer (network precursor); PDMS polydimethylsiloxane).

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term “hyperbranched polymer” as used in this specification,including the claims, is not intended to encompass dendrimers.Dendrimers of a given generation are monodispersed (typically having apolydispersity of less than about 1.02) highly defined globularmolecules, having a degree of branching that is 100%, or very nearly100%. They are prepared by a series of controlled stepwise growthreactions which generally involve protect-deprotect strategies andpurification procedures at the conclusion of each step. As aconsequence, synthesis of dendrimers is a tedious and expensive processthat places a practical limitation on their applicability.

As is the case with all dendritic polymers (including dendrimers,hyperbranched polymers, and the like), hyperbranched polymers arepolymers having branches upon branches. However, in contrast todendrimers, hyperbranched polymers may be prepared in a one-step,one-pot procedure. This facilitates the synthesis of large quantities ofmaterials, at high yields, and at a relatively low cost. Also, theproperties of hyperbranched polymers are different from those ofcorresponding dendrimers due to imperfect branching and rather largepolydispersities, both of which are governed mainly by the statisticalnature of the chemical reactions involved in their synthesis. Therefore,hyperbranched polymers may be viewed as intermediate between traditionalbranched polymers and dendrimers. More specifically, a hyperbranchedpolymer molecule contains a mixture of linear and branched repeatingunits, whereas an ideal dendrimer contains only branched repeatingunits. The degree of branching, which reflects the fraction of branchingsites relative to a perfectly branching system (i.e., an idealdendrimer), for a hyperbranched polymer is greater than 0 and less than1, with typical values being from about 0.25 to about 0.45. Unlike idealdendrimers which have a polydispersity of 1, hyperbranched polymers havetypical polydispersities being greater than 1.1 even at a relatively lowmolecular weight such as 1,000 Daltons, and greater than 1.5 atmolecular weights of about 10,000 or higher. These differences betweenthe polydispersities and degree of branching of hyperbranched polymersand dendrimers are indicative of the relatively higher non-ideality,randomness, and irregularity of hyperbranched polymers as compared withdendrimers, and distinguish hyperbranched polymers from dendrimers.

The hyperbranched polymers of this invention may be prepared by anyapplicable polymerization method, including: (a) monomolecularpolymerization of A_(x)B_(y)C_(z) monomers, wherein A and B are moietiesthat are reactive with each other but not significantly reactive withthemselves, x and y are integers having a value of at least 1 and atleast one of x or y has a value of at least 2, C is a functional groupthat is not significantly reactive with either the A or B moieties oritself during polymerization of the hyperbranched polymer and z is aninteger having a value of 1, or greater; (b) copolymerization orbi-molecular polymerization of A_(x)C_(z) and B_(y) monomers, wherein A,B and C are moieties as defined above, x and y are integers one of whichhaving a value of at least 2 and the other having a value greater than2, and z is an integer having a value of at least 1; and (c)multi-molecular polymerization reactions of two or more polyfunctionalmonomers, wherein the functionality of A or B is at least 2, while thefunctionality of at least one of A or B is higher than 2 (e.g.,A₂+A₂C_(z)+B₃). The invention also encompasses other syntheticstrategies wherein one or more monomers used in the synthesis ofhyperbranched polymers contains a latent functional group or groups thatdo not react significantly under the polymerization conditions. Forexample, two different monomers each having a latent functional group ofthe same or different type can be reacted to form a hyperbranchedpolymer in accordance with this invention (i.e., A_(x)C_(z)+B_(y)C_(w)or A_(x)C_(z)+B_(y)D_(w), wherein A, B, C, x, y, and z are as definedabove, and D is a second kind of latent functional group that does notreact significantly during the A+B polymerization and w is an integerhaving a value of at least 1). Also, a single monomer (e.g.,A_(x)B_(y)C_(z)D_(w)) having x number of A groups and y number of Bgroups that react with each other during the polymerization and z numberof C groups and w number or D groups can be polymerized to form ahyperbranched polymer containing two different types of latentfunctional groups that are not reactive during the A+B polymerizationbut are reactive under another set of conditions. In each of the aboveexamples, at least one of x and y must be an integer equal or greaterthan 2 in order to form a hyperbranched polymer. Other syntheticstrategies that may be employed may include any of the preceding systemsinvolving more than two types of reacting functional groups and/orsystems involving simultaneous polymerization reactions, such asmulti-bond opening or ring opening reactions, step-growthpolycondensations or polyadditions, and chain-growth polymerizations. Ingeneral, in order to allow synthesis and prevent premature reaction ofAB_(x), A_(x)B_(y), A_(x)B_(y)C_(z), A_(x)B_(y)C_(z)D_(w) or the likemonomers, the A and B groups should be unreactive with each other underone set of conditions, such as at normal ambient conditions, butreactive under another set of conditions, such as in the presence of aninitiator, catalyst, heating or other type of activation.

In accordance with one aspect of this invention, a hyperbranchedpolycarbosiloxanes with latent alkoxy functionalities for example may besynthesized by a hydrosilylation polymerization reaction of compoundshaving two or more vinyl, allyl or other homologous functional groupwith a dihydrido- or polyhydrido-silane or siloxane, wherein at leastone of the monomers includes at least three functional groups that arereactive during polymerization conditions and at least one of themonomers includes at least one latent alkoxy functional group that issubstantially unreactive under the polymerization conditions. U.S.patent application Ser. No. 09/753,380, filed Jan. 2, 2001, the contentsof which are incorporated by reference herein, describes synthesis ofvarious hyperbranched polycarbosilanes, polycarbosiloxanes, andpolycarbosilazenes. An example of such a reaction system may berepresented by the following equations:

As illustrated above, the hyperbranched polymers of this invention canbe a copolymer of a first monomer having two or more vinyl or allylreactive functional groups and a second monomer having three or morehydrosilyl reactive functional groups, with at least one of the monomershaving at least one latent functional group (such as OR in the previousequations) that does not react significantly during polymerization ofthe hyperbranched polymer, and with at least one of the monomers havingthree or more reactive functional groups that do react during thepolymerization.

In accordance with a preferred aspect of the invention, the latentfunctional groups that do not react significantly during polymerizationof the hyperbranched polymer may be a hydrolyzable group bonded to asilicon atom. Examples of hydrolyzable groups which can serve as thelatent functional groups of the hyperbranched polymers include halogenatoms, —OR, —OCOR, anhydride and —ON═CR′R″, wherein R, R′ and R″represent an aliphatic or aromatic hydrocarbon group. Preferredhydrolyzable groups include chloro, acetoxy, methoxy and ethoxy groups.

Some specific examples of monomers having vinyl or allyl reactivefunctional groups and latent hydrolyzable groups includedivinyldichlorosilane, 1,3-divinyl-1,3-dimethyl-1,3-dichloro-disiloxane,1,3-divinyltetraethoxydisiloxane, trivinylethoxysilane, andtrivinylmethoxysilane. These monomers can be reacted with monomer havingtwo or more hydrosilyl groups and optionally including latenthydrolyzable groups to produce hyperbranched polymers in accordance withthis invention which have two different types of functional groups,including hydrolyzable groups substantially uniformly distributedthroughout the hyperbranched polymer molecule and either vinyl, allyl orhydrosilyl groups substantially uniformly distributed as terminalend-groups of the hyperbranched polymer molecules.

Examples of monomers having hydrosilyl groups that can be reacted withthe vinyl or allyl functional monomers include hydrosilyl functionalmonomers without latent hydrolyzable groups, such as1,1,3,3-tetramethyldisiloxane, methyltris(dimethylsiloxy)silane,phenyltris(dimethylsiloxy)silane, methylhydrocyclosiloxanes,tetrakis(dimethylsiloxy)silane, dimethylsilane, diethylsilane,diphenylsilane, phenylmethylsilane, methylsilane, phenylsilane, etc.

Examples of monomer containing both hydrosilyl groups and latenthydrolyzable groups include dichlorosilane, dimethoxysilane, etc. Thesemonomers can be reacted with either the above-mentioned monomerscontaining vinyl or allyl functional groups with latent hydrolyzablegroups or with monomers containing vinyl or allyl groups without latenthydrolyzable groups to form the hyperbranched polymers of this inventionhaving at least two different types of functional groups includinghydrolyzable functional groups that are substantially uniformlydistributed throughout the hyperbranched polymer molecule and vinyl,allyl or hydrosilyl functional groups substantially uniformlydistributed as terminal end-groups of the hyperbranched polymermolecule.

Examples of monomers having vinyl or allyl reactive functional groupswithout latent hydrolyzable groups include diallyldimethylsilane,diallyldiphenylsilane, 1,3-diallyltetrakis(trimethylsiloxy)-disiloxane,1,3-diallyltetramethyldisiloxane, divinyldimethylsilane,1,3-divinyl-1,3-diphenyl-1,3-dimethyl-disiloxane,1,5-divinyl-3,3-diphenyltetramethyltrisiloxane,1,5-divinylhexamethyltrisiloxane,1,5-divinyl-3-phenylpentamethyltrisiloxane,divinyltetrakis(trimethylsiloxy)disiloxane, divinyltetramethyldisilane,1,3-divinyltetramethyl-disiloxane, 1,4-divinyltetramethyl-disilylethane,divinyltetraphenyldisiloxane, tris(vinyldimethylsiloxy)methylsilane,tris(vinyldimethylsiloxy)phenylsilane, trivinylmethylsilane,1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane,1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, anddivinyldimethylsilane.

The degree of branching of the hyperbranched polymers used in thisinvention is not critical. However, the degree of branching issufficiently low (e.g., less than 95%, even less than 90%) todistinguish the hyperbranched polymers from dendrimers, which in theideal case have a degree of branching of 100%. The hyperbranchedpolymers used in this invention will typically have a degree ofbranching of from about 20% to about 55%, and more typically from about25% to about 45%. Such hyperbranched polymers can be easily prepared andare relatively inexpensive as compared with dendrimers.

The average degree of branching ({overscore (DB)}) is defined as thenumber average fraction of branching groups per molecule, i.e., theratio of terminal groups plus branched groups to the total number ofterminal groups, branched groups, and linear groups. For ideal dendronsand dendrimers the degree of branching is 1. For ideal linear polymersthe degree of branching is 0. The degree of branching is expressedmathematically as follows:$\overset{\_}{DB} = \frac{N_{t} + N_{b}}{N_{t} + N_{b} + N_{l}}$where N_(t) represents the number of terminal units, N_(b) representsthe number of branched units, and N_(l) represents the number of linearunits, as defined in Hawker, C. J.; Lee, R. Fréchet, J. M. J., J. Am.Chem Soc., 1991, 113, 4583.

The hyperbranched polymers used in this invention may generally have aweight average molecular weight of from about 1000 to about 25,000;preferably from about 2000 to about 20,000; and more preferably fromabout 2000 to about 10,000.

The hyperbranched polymers of this invention may be used for preparingcurable polymer compositions and cured compositions wherein thehyperbranched polymers containing latent functional groups (functionalgroups that do not react significantly during polymerization reactionbut can react under a different set of conditions) are covalently bondedto each other by reaction of the terminal end-groups (e.g., vinyl, allylor hydrosilyl) with a connector or cross-linking agent. In general, thehyperbranched polymers of this invention may be covalently connected toeach other to form a nano-domain-structured network usingalpha,omega-telechelic linear polymers or oligomers, multi-functionallinear polymers with functional groups pendant to the main chainbackbone, and/or multi-functional randomly branched polymers havingfunctional groups regularly or randomly distributed in the main or inthe side chains. Other types of connectors may include di- ormulti-functional low molecular weight non-polymeric compounds that canreact with the terminal functional groups of the hyperbranched polymer.Connectors may also include multi-arm star polymers, dendrimers,dendrons, Combburst™ dendrigrafts, traditional branched polymers,homologously derivatized or other hyperbranched polymers, or otherarchitecturally specific macromolecules. Nano-domained networks formedfrom the hyperbranched polymers of this invention may be viewed asthree-dimensional, cross-linked materials comprising covalently bondednanoscopic, hyperbranched domains which may be of the same or differentchemical composition from the rest of the network, and which containlatent functional groups substantially uniformly distributed throughoutthe volume of the hyperbranched domains. Examples ofalpha,omega-telechelic linear polymers that may be used for connecting(i.e., cross-linking) include those having purely organic, or inorganic(such as siloxane), or organo-inorganic (such as carbosilane), backbone,with specific examples including polysiloxanes, such aspolydimethylsiloxane, and having appropriate terminal functional groupsthat will react with the terminal functional groups of the hyperbranchedpolymer molecules.

In accordance with a preferred aspect of this invention, curablecompositions can be prepared by combining the hyperbranched polymerswith the connectors or cross-linkers. Depending on the selection of thehyperbranched polymer or hyperbranched polymers and connectors orcross-linkers, and other additives, various coating compositions,adhesives, sealents, films, sheets, membranes or other objects may beprepared. Such compositions may be prepared as one-part systems well inadvance of their use, or as two-part systems that are combined justprior to use.

Depending on the chemistry utilized, initiators and catalysts may beincluded in the composition in effective amounts as appropriate.Depending on the type of composition that is being produced, fillers,pigments, dies, antioxidants, fiber or particulate reinforcing agents,impact modifying agents, UV stabilizers, and the like may be added ineffective amounts. In certain applications, it may be desirable to addsmall amounts of solvents.

The curable compositions of this invention may contain one hyperbranchedpolymer or a combination of two or more different hyperbranched polymershaving the same or different chemical structure and having the same ordifferent terminal groups. Similarly, the curable compositions maycontain a single connector or cross-linking agent, or a combination oftwo or more connectors/cross-linking agents.

The cured (cross-linked) nano-domain-structured networks may or may notcomprise domains of different chemical composition. However,architectural differences may result in different relative densities,shapes and sizes. Some of these structural features can be controlled byappropriate selection of precursor moieties and by the reactionconditions employed. In general, the relative size of hyperbranchedpolymers are smaller (ranging from about 1 to about 5, 10, or 15 nm)than their linear counterparts of equivalent molecular weight. Theresulting three-dimensional cross-linked materials comprise covalentlybonded nanoscopic, hyperbranched domains which may be of the same ordifferent chemical compositions than the linear polymers comprising therest of the network. These materials may be formed into films, sheets,membranes, coatings or other objects, and may exhibit glass transitiontemperatures that may rank them among either elastomers or plastomers.These and other properties of these networks depend on the selection ofprecursor polymers, including their chemical composition, moleculararchitecture, molecular weight and molecular weight distribution. Thematerials may also exhibit high thermal stability, mechanical strengthand toughness, and offer new ways for preparing specialty membranes,protective coatings, photoresists, novel composites, controlled porositymaterials, etc.

A particularly interesting use for the hyperbranched polymers of thisinvention (especially polycarbosilanes, polycarbosiloxanes,polycarbosilazenes and copolymers thereof) is in the preparation ofgaskets, o-rings, sealents, and sealing coatings exhibiting elasticity,heat resistance, and other properties comparable to conventionalsilicone compositions, but exhibiting improved mechanical properties(e.g., tensile strength and abrasion resistance) that are superior toconventional silicone compositions. In accordance with this aspect ofthe invention, latent hydrolyzable groups (e.g., ethoxy) substantiallyuniformly distributed throughout the volume of the hyperbranched domainsmay be reacted, such as with water, to undergo hydrolysis andcondensation to form nanoscopic silica-like inorganic structuredistributed throughout the hyperbranched domains. To increase thecross-link density of these structures, co-reactants, such astetraethoxysilane (TEOS), may be added into the domains containinglatent hydrolyzable groups either before or after the A+B polymerizationreaction. These nano-scaled silica-like, particle-like structures serveas in situ formed reinforcing agents that improve the mechanicalproperties of the composition. It is generally known that theimprovement in mechanical properties achieved with inorganic particulatereinforcing agents is inversely related to the average diameter of thereinforcing particles. In the scope of this invention, the inorganicparticle-like reinforcing structures have dimensions on the order offrom about 1 to about 5, 10, or 15 nm. Additionally, the inorganicsilica reinforcing structures of this invention are very uniformlydistributed throughout the hyperbranched domains and are covalentlybonded thereto, and therefore significantly improve the mechanicalproperties of the cured compositions of this invention. An illustrationof this procedure is shown in FIG. 1.

EXAMPLES Example 1 Preparation of Dual Functionalized HyperbranchedPoly(carbosiloxane) HB-DVSi₂(OEt)₄DS-TDMSS-SiMe₂H with ReactiveEthoxysilyl and Hydrosilane Groups from (CH₂═CHSi (OEt)₂)₂O andSi(OSiMe₂H)₄ (an A₂B₄+C₄ System)

A 250 ml two-necked, round-bottomed flask equipped with a verticalcooling condenser was charged with 0.1550 gPlatinum-divinyltetramethyldisiloxane complex in xylene (Karstedtcatalyst, ˜2% platinum in xylene). The flask was flushed with N₂ for 1min. A mixture of 1,3-divinyltetraethoxyldisiloxane (30.00 g, 95%, 92.98mmol) and tetrakis(dimethylsiloxy)silane (45.83 g, 139.40 mmol) waspoured into the two-necked, round-bottomed flask with stirring. Theresulting mixture was stirred at room temperature for 40 min., and thenheated in an oil bath kept at 50° C. for 16 h. The obtained viscous oilwas washed by acetonitril (50×3 ml). The volatiles were stripped off byrotvap in vacuum, and they were further dried in vacuo for 16 h to givea slightly yellowish oil (63 g). ¹H NMR in CDCl₃: 0.051 ppm (s, SiCH₃),0.056 ppm (s, SiCH₃), 0.065 ppm (s, SiCH₃), 0.112 ppm (s, SiCH₃), 0.119ppm (s, SiCH₃), 0.158 ppm (s, SiCH₃), 0.168 ppm (s, SiCH₃), 0.178 ppm(s, SiCH₃), 0.53-0.57 ppm (broad, m, CH₂CH₂), 1.09 ppm (d, CH ₃CH, J7.324 Hz, trace amount), 1.18 ppm (t, OCH₂ CH ₃, J 6.592 Hz), 3.78 ppm(q, OCH ₂CH₃, J 6.837 Hz), 4.68 ppm (m, SiH). ¹³C{¹H} NMR in CDCl₃:−1.13 ppm (s, SiCH₃), 0.13 ppm (s, SiCH₃), 2.75 ppm (s, SiCH₃), 6.54 ppm(s, CH₂CH₂), 7.39 ppm (s, CH₂CH₂), 8.79 ppm (s, CH₂CH₂), 18.05 (s, OCH₂CH₃), 57.96 ppm (s, OCH₂CH₃). ²⁹Si{¹H} NMR in CDCl₃: (−150.6)-(−104.0)ppm [m, Si(O—)₄], (−54.4)-(−52.7) ppm [m, Si(OEt)₂], (−6.6)-(−5.5) ppm(m, SiH), 8.9-10.1 ppm [m, Si(CH₃)₂]. IR on KBr disc (selectedresonance): 2133 cm⁻¹ [ν(SiH)], 960 cm⁻¹ [ν(Si—O—C₂H₅)]. GPC (Columnset: polymer lab columns 300×7.5 Plgel 10 u mixed 10 M-MIXED-34-23, 10M-M34-2, Plgel 100 A, Plgel 50 A. Solvent: toluene. Standard:polystyrene 800-300,000): Mn 2809, Mw 7540, Polydispersity 2.68.

Example 2 Curing of HB-DVSi₂(OEt)₄DS-TDMSS-SiMe₂H of Example 1 withAlpha,Omega-Telechelic Vinyl-Terminated Polydimethylisloxane

CH₂═CHSiMe₂O(SiMe₂O)_(n)SiMe₂CH═CH₂(MW 62,700, 1.20 g) was dissolved in3.5 mL hexanes in a 15 mL vial. To the solution were added and dissolvedin following sequence: 0.1 mL hexanes solution of 3-methyl-1-pentyn-3-ol(0.30 g/mL); 0.1 mL hexanes solution ofplatinum—divinyltetramethyldisiloxane complex in xylene (Karstedtcatalyst, ˜2% platinum in xylene) (0.2 g xylene solution in 1 mLhexanes); HB-DVSi₂(OEt)₄DS-TDMSS-SiMe₂H (0.30 g); and 0.1 g titaniumdi-n-butoxide(bis-2,4-pentanedionate) (73% in butanol). The resultingsolution was cast onto a Ti coated PET plate which was wet by (EtO)₄Siand dried in the air prior casting, and the coating was cured at 120° C.for 20 min to yield an insoluble slightly yellowish coating.

Example 3 Curing of HB-DVSi₂(OEt)₄DS-TDMSS-SiMe₂H Example of 1 With TwoAlpha,Omega-Telechelic Vinyl-Terminated Polydimethylsiloxanes (MW 62,700and MW 165,000)

CH₂═CHSiMe₂O(SiMe₂O)_(n)SiMe₂CH═CH₂ (MW 62,700, 0.9 g) andCH₂═CHSiMe₂O(SiMe₂O)_(n)SiMe₂CH═CH₂ (MW 165,000, 0.9 g) were dissolvedin 8 mL hexanes in a 20 mL vial. To the solution were added anddissolved in the following sequence: 0.15 mL hexanes solution of3-methyl-1-pentyn-3-ol (0.20 g/mL); 0.15 mL hexanes solution ofplatinum—divinyltetramethyldisiloxane complex in xylene (Karstedtcatalyst, ˜2% platinum in xylene) (0.20 g xylene solution in 1 mLhexanes); HB-DVSi₂(OEt)₄DS-TDMSS-SiMe₂H (0.45 g); 0.05 g titaniumdi-n-butoxide(bis-2,4-pentanedionate) solution (73% in butanol), and 0.2mL THF solution of (3-glycidoxypropyl)dimethylethoxysilane (0.25 g/ml).The resulting solution was cast onto a Ti coated PET plate, and cured at150° C. for 20 min to yield an insoluble slightly yellowish coating.

Example 4 Curing of HB-DVSi₂(OEt)₄DS-TDMSS-SiMe2H Example of 1 with TwoAlpha,Omega-Telechelic Vinyl-Terminated Polydimethylsiloxanes (MW 62,700and MW 165,000) and Post-Treatment with tetraethyl orthosilicate

CH₂═CHSiMe₂O(SiMe₂O)_(n)SiMe₂CH═CH₂ (MW 62,700, 8 g) andCH₂═CHSiMe₂O(SiMe₂O)_(n)SiMe₂CH═CH₂ (MW 165,000, 8 g) were dissolved in20 mL hexanes in a 250 mL beaker. To the solution were added anddissolved in following sequence: 1.2 g 3-methyl-1-pentyn-3-ol; 0.20 gplatinum—divinyltetramethyldisiloxane complex in xylene (Karstedtcatalyst, ˜2% platinum in xylene); 4.0 g HB-DVSi₂(OEt)₄DS-TDMSS-SiMe₂H;and 1.2 g titanium di-n-butoxide(bis-2,4-pentanedionate) solution (73%in butanol). Most volatiles were removed by blowing N₂ at the surface ofthe formulation. The resulting viscous solution was cast onto a mold anddried in the air for 4 days. It was then cured at 55° C. for 1 hour, 80°C. for 1.5 h, 155° C. for 1 hour to give a yellow brownish rubber, freeof air bubbles. Shore A durometer showed average reading 31.4. Theobtained silicone rubber was soaked in tetraethyl orthosilicate for 16hours, and kept at 150° C. in an oven for 1 hour to give a tougherelastic rubber. Shore A durometer showed average reading 40.

The above description is considered that of the preferred embodimentsonly. Modifications of the invention will occur to those skilled in theart and to those who make or use the invention. Therefore, it isunderstood that the embodiments described above are merely forillustrative purposes and are not intended to limit the scope of theinvention, which is defined by the following claims as interpretedaccording to the principles of patent law, including the doctrine ofequivalents.

1. A cross-linked polymer network, comprising: hyperbranched polymerdomains having a plurality of each of at least one type of potentiallyreactive functional groups, wherein at least one of the different typesof potentially reactive function groups being a hydrolyzable groupsubstantially uniformly distributed throughout the hyberbranched polymerdomains; and a cross-linker covalently bonding the hyperbranched polymerdomains together.
 2. The network of claim 1, wherein at least one of thedifferent types of potentially reactive functional groups is ahydrolyzable group bonded to a silicon atom substantially uniformlydistributed throughout the hyperbranched polymer domains.
 3. The networkof claim 1, wherein the hyperbranched polymer is a product of apolymerization reaction of a first monomer having two or more reactivefunctional groups of the first type (A) and a second monomer having twoor more reactive functional groups of the second type (B), at least oneof the monomers having three or more reactive functional groups and atleast one of the monomers having at least one latent functional group(C) that does not react significantly during the polymerization of thehyperbranched polymer.
 4. The network of claim 1, wherein thehyperbranched polymer is a product of a polymerization reaction of afirst monomer having two or more vinyl or allyl reactive functionalgroups (A) and a second monomer having two or more hydrosilyl reactivefunctional groups (B), at least one of the monomers having three or morereactive functional groups and at least one of the monomers having atleast one latent functional group (C) that does not react significantlyduring the polymerization of the hyperbranched polymer.
 5. The networkof claim 1, wherein the hyperbranched polymer is a product of apolymerization reaction of a monomer having at least one reactivefunctional group of the first type (A), at least two reactive functionalgroups of the second type (B) and at least one latent functional group(C) that does not react significantly during the polymerization of thehyperbranched polymer.
 6. The network of claim 1, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least one hydrosilyl reactive functional group (A), atleast two vinyl or allyl reactive functional groups (B) and at least onelatent functional group (C) that does not react significantly during thepolymerization of the hyperbranched polymer.
 7. The network of claim 1,wherein the hyperbranched polymer is a product of a polymerizationreaction of a monomer having at least one vinyl or allyl reactivefunctional group (A), at least two hydrosilyl reactive functional groups(B) and at least one latent functional group (C) that does not reactsignificantly during the polymerization of the hyperbranched polymer. 8.The network of claim 1, wherein the hyperbranched polymer is a productof a polymerization reaction involving more than two mutually reactivemonomers wherein at least one of the monomers has two or more reactivefunctional groups of the first type (A) and at least one of the othermonomers has three or more reactive functional groups of the second type(B), at least one of the monomers having at least one latent functionalgroup (C) that does not react significantly during the polymerization ofthe hyperbranched polymer.
 9. The network of claim 1, wherein thehyperbranched polymer is a product of a polymerization reaction of afirst monomer having two or more reactive functional groups of the firsttype (A) and a second monomer having two or more reactive functionalgroups of the second type (B), at least one of the monomers having threeor more reactive functional groups and wherein one of the monomershaving at least one latent functional group (C) and the other monomerhaving at least one latent functional group (D) wherein these latentfunctional groups will react with each other under the reactionconditions that are different from the polymerization reactionconditions.
 10. The network of claim 1, wherein the hyperbranchedpolymer is a product of a polymerization reaction of a monomer having atleast one reactive functional group of the first type (A), at least tworeactive functional groups of the second type (B) and at least twolatent functional groups (C and D) that do not react significantlyduring the polymerization of the hyperbranched polymer but will reactwith each other under the reaction conditions that are different fromthe polymerization reaction conditions.
 11. The network of claim 1,wherein the hyperbranched polymer is a product of a polymerizationreaction involving more than two mutually reactive monomers wherein atleast one of the monomers has two or more reactive functional groups ofthe first type (A) and at least one of the other monomers having threeor more reactive functional groups of the second type (B), at least oneof the monomers having at least two latent functional group (C and D) orat least one of the reacting monomers having one type of latentfunctional groups (C) while at least one of the other monomers having atleast one of another reactive functional groups (D) wherein the latentfunctional groups (C and D) do not react significantly during thepolymerization of the hyperbranched polymer but will react with eachother under the reaction conditions that are different from thepolymerization reaction conditions.
 12. The network of claim 1, whereinthe hyperbranched polymer is a product of a polymerization reaction of amonomer having two or more hydrosol groups, and a monomer selected fromthe group consisting of diallyldimethylsilane, diallyldiphenylsilane,1,3-diallyltetrakis(trimethylsiloxy)-disiloxane,1,3-diallyltetramethyldisiloxane, divinyldimethylsilane,1,3-divinyl-1,3-diphenyl-1,3-dimethyl-disiloxane,1,5-divinyl-3,3-diphenyltetramethyltrisiloxane,1,5-divinylhexamethyltrisiloxane,1,5-divinyl-3-phenylpentamethyltrisiloxane,divinyltetrakis(trimethylsiloxy)disiloxane, divinyltetramethyldisilane,1,3-divinyltetramethyldisiloxane, 1,4-divinyltetramethyldisilylethane,divinyltetraphenyldisiloxane, tris(vinyldimethylsiloxy)methylsilane,tris(vinyldimethylsiloxy)phenylsilane, trivinylmethylsilane,1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane,1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, anddivinyldimethylsilane.
 13. The network of claim 1, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least two vinyl or allyl groups, and a monomerselected from the group consisting of 1,1,3,3-tetramethyldisiloxane,methyltris(dimethylsiloxy)silane, phenyltris(dimethylsiloxy)silane,methylhydrocyclosiloxanes, tetrakis(dimethylsiloxy)silane,dimethylsilane, diethylsilane, diphenylsilane, phenylmethylsilane,methylsilane, and phenylsilane.
 14. The network of 1, wherein thecross-linker is an alpha, omega-telechelic linear polymer or oligomer.15. The network of claim 14, wherein the alpha, omega-telechelic linearpolymer or oligomer has a polysiloxane backbone.
 16. The network ofclaim 14, wherein the alpha, omega-telechelic linear polymer or oligomeris a polydialkylsiloxane.
 17. The network of claim 1, wherein thecross-linker is a multi-functional linear polymer with functional groupspendant to the main chain backbone.
 18. The network of claim 1, whereinthe cross-linker is a multi-functional traditional branched polymerhaving functional groups regularly or randomly distributed in the mainor in the side chains.
 19. The network of claim 1, wherein thecross-linker is a di- or multi-functional non-polymeric compound thatcan react with the potentially reactive functional groups of thehyperbranched polymer.
 20. The network of claim 1, wherein thecross-linker is selected from the group consisting of multi-arm starpolymers, dendrimers, dendrons, dendrigrafts and hyperbranched polymers.21. The network of claim 1, wherein crosslinking of the hyperbranchedpolymer was achieved by the hydrolysis of functional groups of thehyperbranched polymer molecules.
 22. A process for making a cross-linkedpolymer network, comprising the step of: reacting a hyperbranchedpolymer having a plurality of each of at least two different types offunctional groups with a cross-linker that covalently bonds thehyperbranched polymer molecules together, wherein at least one of thedifferent types of functional groups is a hydrolyzable group bonded to asilicon atom substantially uniformly distributed throughout thehyperbranched polymer molecule and the other of the different functionalgroups is substantially uniformly distributed at the terminals of thehyperbranched polymer molecule.
 23. The process of claim 22, wherein atleast one of the different types of functional groups is substantiallyuniformly distributed throughout the hyperbranched polymer molecule andat least one other of the two different functional groups issubstantially uniformly distributed at the terminals of thehyperbranched polymer molecule.
 24. The process of claim 22, wherein atleast one of the different types of functional groups is a hydrolyzablegroup substantially uniformly distributed throughout the hyperbranchedpolymer molecule and the other of the different functional groups is ahydrosilyl, vinyl or allyl group.
 25. The process of claim 22, whereinthe hyperbranched polymer is a product of a polymerization reaction of afirst monomer having two or more reactive functional groups of the firsttype (A) and a second monomer having two or more reactive functionalgroups of the second type (B), at least one of the monomers having threeor more reactive functional groups and at least one of the monomershaving at least one latent functional group (C) that does not reactsignificantly during the polymerization of the hyperbranched polymer.26. The process of claim 22, wherein the hyperbranched polymer is aproduct of a polymerization reaction of a first monomer having two ormore vinyl or allyl reactive functional groups (A) and a second monomerhaving two or more hydrosilyl reactive functional groups (B), at leastone of the monomers having three or more reactive functional groups andat least one of the monomers having at least one latent functional group(C) that does not react significantly during the polymerization of thehyperbranched polymer.
 27. The process of claim 22, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least one reactive functional group of the first type(A), at least two reactive functional groups of the second type (B) andat least one latent functional group (C) that does not reactsignificantly during the polymerization of the hyperbranched polymer.28. The process of claim 22, wherein the hyperbranched polymer is aproduct of a polymerization reaction of a monomer having at least onehydrosilyl reactive functional group (A), at least two vinyl or allylreactive functional groups (B) and at least one latent functional group(C) that does not react significantly during the polymerization of thehyperbranched polymer.
 29. The process of claim 22, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least one vinyl or allyl reactive functional group(A), at least two hydrosilyl reactive functional groups (B) and at leastone latent functional group (C) that does not react significantly duringthe polymerization of the hyperbranched polymer.
 30. The process ofclaim 22, wherein the hyperbranched polymer is a product of apolymerization reaction involving more than two mutually reactivemonomers wherein at least one of the monomers has two or more reactivefunctional groups of the first type (A) and at least one of the othermonomers has three or more reactive functional groups of the second type(B), at least one of the monomers having at least one latent functionalgroup (C) that does not react significantly during the polymerization ofthe hyperbranched polymer.
 31. The process of claim 22, wherein thehyperbranched polymer is a product of a polymerization reaction of afirst monomer having two or more reactive functional groups of the firsttype (A) and a second monomer having two or more reactive functionalgroups of the second type (B), at least one of the monomers having threeor more reactive functional groups and wherein one of the monomershaving at least one latent functional group (C) and the other monomerhaving at least one latent functional group (D) wherein these latentfunctional groups will react with each other under the reactionconditions that are different from the polymerization reactionconditions.
 32. The process of claim 22, wherein the hyperbranchedpolymer is a product of a polymerization reaction of a monomer having atleast one reactive functional group of the first type (A), at least tworeactive functional groups of the second type (B) and at least twolatent functional groups (C and D) that do not react significantlyduring the polymerization of the hyperbranched polymer but will reactwith each other under the reaction conditions that are different fromthe polymerization reaction conditions.
 33. The process of claim 22,wherein the hyperbranched polymer is a product of a polymerizationreaction involving more than two mutually reactive monomers wherein atleast one of the monomers has two or more reactive functional groups ofthe first type (A) and at least one of the other monomers having threeor more reactive functional groups of the second type (B), at least oneof the monomers having at least two latent functional group (C and D) orat least one of the reacting monomers having one type of latentfunctional groups (C) while at least one of the other monomers having atleast one of another reactive functional groups (D) wherein the latentfunctional groups (C and D) do not react significantly during thepolymerization of the hyperbranched polymer but will react with eachother under the reaction conditions that are different from thepolymerization reaction conditions.
 34. The process of claim 22, whereinthe hyperbranched polymer is a product of a polymerization reaction of amonomer having two or more hydrosilyl groups, and a monomer selectedfrom the group consisting of diallyldimethylsilane,diallyldiphenylsilane, 1,3-diallyltetrakis(trimethylsiloxy)-disiloxane,1,3-diallyltetramethyldisiloxane, divinyldimethylsilane,1,3-divinyl-1,3-diphenyl-1,3-dimethyl-disiloxane,1,5-divinyl-3,3-diphenyltetramethyltrisiloxane,1,5-divinylhexamethyltrisiloxane,1,5-divinyl-3-phenylpentamethyltrisiloxane,divinyltetrakis(trimethylsiloxy)disiloxane, divinyltetramethyldisilane,1,3-divinyltetramethyldisiloxane, 1,4-divinyltetramethyldisilylethane,divinyltetraphenyldisiloxane, tris(vinyldimethylsiloxy)methylsilane,tris(vinyldimethylsiloxy)phenylsilane, trivinylmethylsilane,1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane,1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, anddivinyldimethylsilane.
 35. The process of claim 22, wherein thehyperbranched polymer is a product of a polymerization reaction of amonomer having at least two vinyl or allyl groups, and a monomerselected from the group consisting of 1,1,3,3-tetramethyldisiloxane,methyltris(dimethylsiloxy)silane, phenyltris(dimethylsiloxy)silane,methylhydrocyclosiloxanes, tetrakis(dimethylsiloxy)silane,dimethylsilane, diethylsilane, diphenylsilane, phenylmethylsilane,methylsilane, and phenylsilane.
 36. The process of claim 22, wherein thecross-linker is an alpha, omega-telechelic linear polymer.
 37. Theprocess of claim 36, wherein the alpha, omega-telechelic linear polymeror oligomer has a polysiloxane backbone.
 38. The process of claim 36,wherein the alpha, omega-telechelic linear polymer or oligomer is apolydialkylsiloxane.
 39. The process of claim 22, wherein thecross-linker is a multi-functional linear polymer with functional groupspendant to the main chain backbone.
 40. The process of claim 22, whereinthe cross-linker is a multi-functional traditional branched polymerhaving functional groups regularly or randomly distributed in the mainor in the side chains.
 41. The process of claim 22, wherein thecross-linker is a di- or multi-functional non-polymeric compound thatcan react with the terminal functional groups at the surface of thehyperbranched polymer.
 42. The process of claim 22, wherein thecross-linker is selected from the group consisting of multi-arm starpolymers, dendrimers, dendrons, dendrigrafts and hyperbranched polymers.43. The process of claim 22, wherein the crosslinking of thehyperbranched polymer is achieved by the hydrolysis of functional groupsthat were substantially uniformly distributed at the terminals of thehyperbranched polymer molecules.